US5571768AExpiredUtility

Zeolite functionalized with organosiliceous groups

82
Assignee: MOBIL OIL CORPPriority: Mar 12, 1992Filed: Sep 15, 1994Granted: Nov 5, 1996
Est. expiryMar 12, 2012(expired)· nominal 20-yr term from priority
Inventors:Clarence D. ChangPaul G. Rodewald
B01J 31/125C07C 6/123C07C 5/41C07C 1/20C07C 2529/40B01J 29/44C10G 45/64C07C 5/2708C07C 2/12C07C 45/54Y02P20/584B01J 31/40C07C 6/126B01J 2229/12C07C 2/66B01J 29/40C10G 50/00B01J 2229/42B01J 31/0274
82
PatentIndex Score
40
Cited by
15
References
40
Claims

Abstract

There is provided a zeolite, such as ZSM-5, which is functionalized with at least one organosiliceous group of the formula, SiRn(OX)4-n, where R is at least one hydrocarbyl group, n is 1 or 2 and X is Si or H. There is also provided a method for functionalizing a zeolite by treatment with a silicone compound, such as hexamethyldisiloxane, under vapor phase conditions. This contacting may take place in the presence of hydrogen and an organic carrier. The functionalized zeolites may provide a catalyst which is both highly active and highly selective for converting aromatic hydrocarbons, especially alkylbenzene compounds, to products comprising the para-isomer of dialkylbenzenes. The disproportionation of toluene is an example of such a reaction.

Claims

exact text as granted — not AI-modified
What is claimed is: 
     
       1. A zeolite functionalized with at least one organosiliceous group of the formula, SiR n  (OX) 4-n , where R is at least one hydrocarbyl group, n is 1 or 2 and X is Si or H. 
     
     
       2. A zeolite according to claim 1, wherein R is an alkyl or aryl group having from 1 to 10 carbon atoms. 
     
     
       3. A zeolite according to claim 2, wherein R is a methyl or phenyl group. 
     
     
       4. A zeolite according to claim 1, where R is a methyl group. 
     
     
       5. A zeolite according to claim 1 having a silica to alumina molar ratio of at least 20. 
     
     
       6. A zeolite according to claim 5 having a silica to alumina molar ratio of 60 or less. 
     
     
       7. A zeolite according to claim 6 having a Constraint Index of from 1 to 12. 
     
     
       8. A zeolite according to claim 6 which is ZSM-5 functionalized with at least one group of the formula, Si(CH 3 ) 2  (OX) 2 , and functionalized with at least one group of the formula, Si(CH 3 )(OX) 3 , where X is Si or H. 
     
     
       9. A zeolite according to claim 8 having a sorption capacity for n-hexane of at least 6 wt. %. 
     
     
       10. A zeolite according to claim 5, wherein said organosiliceous groups are located substantially on the external surface of said zeolite. 
     
     
       11. A zeolite according to claim 6 which is combined with a binder material. 
     
     
       12. A zeolite according to claim 8 which is combined with a silica binder. 
     
     
       13. A zeolite according to claim 1 which has been functionalized with said organosiliceous group by contacting the zeolite with a silicone compound having at least two silicon atoms per molecule. 
     
     
       14. A zeolite according to claim 13, wherein said silicone compound is of the formula ##STR5## where R 1 , R 2 , R 3 , R 4 , R 5 , and R 6  are independently methyl or phenyl and m is from 1 to 10. 
     
     
       15. A zeolite according to claim 14, wherein said silicone compound is selected from the group consisting of hexamethyldisiloxane, decamethyltetrasiloxane and diphenyltetramethyldisiloxane. 
     
     
       16. A zeolite according to claim 13, wherein said silicone compound is selected from the group consisting of octamethylcyclotetrasiloxane and decamethylcyclo-pentasiloxane. 
     
     
       17. A zeolite according to claim 13 which has been functionalized by contacting the zeolite with said silicone compound under vapor phase conditions in the presence of hydrogen. 
     
     
       18. A zeolite according to claim 17 which has been functionalized by contacting the zeolite with said silicone compound under vapor phase conditions in the presence of an organic carrier. 
     
     
       19. A zeolite according to claim 18, wherein said organic carrier is toluene. 
     
     
       20. A method for preparing a zeolite according to claim 1, said method comprising reacting said zeolite with a silicone compound under vapor phase conditions, said silicone compound having at least two silicon atoms, the silicon atoms being connected to one another through oxygen atoms, the remainder of the bonds extending from the silicon atoms being connected to hydrocarbyl groups having from 1 to 10 carbon atoms. 
     
     
       21. A method according to claim 20, wherein the silicon and oxygen atoms in said silicone compound form a cyclic structure. 
     
     
       22. A method according to claim 21, wherein said silicone compound is selected from the group consisting of octamethylcyclotetrasiloxane and decamethylcyclo-pentasiloxane. 
     
     
       23. A method according to claim 20, wherein said silicone compound has the formula ##STR6## where R 1 , R 2 , R 3 , R 4 , R 5 , and R 6  are independently methyl or phenyl and m is from 1 to 10. 
     
     
       24. A method according to claim 23, wherein said silicone compound is selected from the group consisting of hexamethyldisiloxane, decamethyltetrasiloxane and diphenyltetramethyldisiloxane. 
     
     
       25. A method according to claim 20, wherein said zeolite has a silica to alumina molar ratio of at least 20. 
     
     
       26. A method according to claim 25, wherein said zeolite has a silica to alumina molar ratio of 60 or less. 
     
     
       27. A method according to claim 26, wherein said zeolite has a Constraint Index of from 1 to 12. 
     
     
       28. A method according to claim 20, wherein said zeolite is ZSM-5. 
     
     
       29. A method according to claim 26, wherein said zeolite is ZSM-5. 
     
     
       30. A method according to claim 20, wherein said zeolite is combined with a binder material prior to contact with said silicone compound. 
     
     
       31. A method according to claim 28, wherein said zeolite is combined with a silica binder material prior to contact with said silicone compound. 
     
     
       32. A method according to claim 29, wherein said zeolite is combined with a silica binder material prior to contact with said silicone compound. 
     
     
       33. A method according to claim 20, wherein said zeolite is contacted with an organosilicon compound, followed by calcination in an oxygen containing atmosphere, prior to contact of said zeolite with said silicone compound. 
     
     
       34. A method according to claim 20, wherein said zeolite is contacted with said silicone compound in the presence of hydrogen and an organic carrier. 
     
     
       35. A method according to claim 34, wherein said organic carrier is toluene. 
     
     
       36. A method according to claim 29, wherein said silicone compound is hexamethyldisiloxane. 
     
     
       37. A method according to claim 29, wherein said silicone compound is decamethyltetrasiloxane. 
     
     
       38. A method according to claim 29, wherein said silicone compound is diphenyltetramethyldisiloxane. 
     
     
       39. A method according to claim 29, wherein said silicone compound is octamethylcyclotetrasiloxane. 
     
     
       40. A method according to claim 29, wherein said silicone compound is decamethylcyclopentasiloxane.

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